Treating porous and nonporous materials



Patented Nov. 4, 1930 UNITED STATES PATENT OFFICE THEODORE I. BRADLEY,OF WESTFIELD, NEW JERSEY, ASSIGNOR TO AMERICAN G Y- ANAM D COMPANY, OFNEW YORK, N. Y., A CORPORATION OF MAINE TREATING POROUS AND NONPOROUSMATERIALS No Drawing.

This invention relates to processes of treating bodies. such as porousmaterials or materials having a porous surface, and relates moreparticularly to a treatment of such ma- 5 terials with new types ofpolybasic acidpolyhydric alcohol condensation products which arewater-soluble.

Porous and non-porous bodies have previously been coated or impregnatedwith various materials, including resinous condensation productsof-polybasic acids with polyhydrlc alcohols. However, these resinousproducts are only soluble in certain organic solvents or solventmixtures and their use in this connection with such solvents is anexpensive and otherwise undesirable procedure.

It is one of theobjects of the present invention to coat or impregnatein whole or in part, non-porous and porous bodies with syn- 0 theticresinous materials without necessitating the employment of organicsolvents or solvent mixtures. 1tis a further object to treat thesebodies with synthetic resins which may be dissolved in water and-whichmay later be converted into water-insoluble resins.

I have discovered that these and other objects may be attained bytreating such bodies with a water solution of a material formed by thechemical combination of a water-insoluble, resinous polyhydricalcohol-polybasic acid condensation product with a watersoluble basicmaterial.

As described in my copending application, Serial #403,903, of which thisis a continuation in part, these water-soluble resins may be preparedfrom a. large number of substances and the details of operation may bevaried in many ways. As a specific example of a resin suitable for thepurposes of the present invention, the following is 'given merely forpurposes of illustr'ationand not in limitation Example A Parts by weight96% g lycerol Phthalic anhydride 148 Total 211 This mixture may beheated in any suitable container, aluminum apparatus being Serial No.409,768.

preferable, to a temperature of from 150 to 230 C. until a sample uponcooling sets to a hard, non-sticky resin having a softening point ofabout 85 to 100 C., as determined by the A. S. T. M. ball and ringmethod, and an acid number of from 100 to 150. The exact time of heatingwill vary somewhat according to the temperatures employed, and the rateof heat transfer of the containing vessels. Considerable latitude in thedegree of hardness. of softening point, or of acid number is permissiblein the first stage of the present invention. The main limiting factor isthe acid number of the resin, since if this falls too low, say, lessthan about 50, the resins generally cannot be rendered as soluble inwater as might be desired for some commercial uses.

()ne phthalic glyceride resin made in accordance with this procedure wasfound to have an acid number of 100 and a softening point of 87.5 C.This resin was rendered water soluble in the second or B stage of theprocess as follows:

This mixture was agitated in a closed vessel at room temperature forseveral hours until the resin had dissolved in the water to form aclear, transparent solution. The same results were likewise obtained ina shorter period of time by effecting solution at elevated temperatures.

The B stage of the process was repeated with other portions of thephthalic glyceride resin, substituting sodium and potassium hydroxidesin chemically equivalent proportions for the ammonium hydroxide, withequally good results, clear and complete solution being effected.Similar results were also obtained by substituting water-soluble organicbases, i. e. the ethanolamines, etc, for the inorganic bases.

Solution B pre ared as above described, was applied by owing it uponsheets of highade tissue paper. The paper was then diied at atemperature of about 80 C. for a period of about ten minutes. The pa rso treated was transparent and had a hlgh degree of flexibility. Toimprove water resistance, the resin absorbed by the paper was renderedcompletely water-insoluble by treating the impregnated paper with asolution of dilute acetic acid and then drying.

As examples of other resinous esters suitable for use in my process,which may be obtained by combining polyhydric alcohols with (polybasiccarboxylic acids alone, or admixe with monobasic acids, etc., thefollowing are illustrative:

Example 0 Parts by weight I Diethylene glycol 106 Phthalic an ydride 148Total 254 This was heated at 230- C. until"a sample showed the acidnumber to be 99.7. An aqueous solution was efiected by agitation of thefollowing mixture at room temperature:

This was heated at 180 C. until a sample was quite viscous and showed anacid number of 229.5. Solution in water was effected by agitation of:

26.4 parts by weight-" resin D 18.2 parts by weight water 6.0 parts byweight-" potassium hydroxide 50.6 Total This highly viscous but completesolution gbas Efiected by agitation at a temperature of Example E I:51:13 Glycerol 98%-; 69 Phthalic anhydride 160 Stearic acid 15 Total 244- This was heated at 225 C. until a sample showed the acid number tobe 134 and the softening point 71.5 C. Solution was effected byagitation of:

parts by weight of resin E 200 parts by weight of water This was heatedat 220230 C. until a roduct was obtained having an acid numr of 92.8 anda softening Solution was efiected by agitation of:

200 parts by weight of resin F 570 parts by weight of water 30, parts byweight of concentrated ammonium hydroxide 86 j Total This solution had aviscosity of 1.40 oises at 25 C. which was found to be reduce upon theaddition of more water. These solutions were found to dry quickly whenapplied to a surface or used as an impregnum, and subsequently becamewater-insoluble, even at ordinary room temperatures. Heating or bakingat elevated tem eratures hastens conversion into the insolu le form.

Resin F and coatings derived therefrom may be rendered softer and ofincreased flexibility by increasing the content of fatty acid and/or bythe use of glycols to replace, partially or wholly, the glycerol.

These examples merely serve to show the wide applicability of thisprocess of solubilization to the whole range of resinous esters whichmay be derived from polyhydric alcohols such as ethylene glycol and itshigher homologues, di-ethylene glycol and its higher homologues,glycerol, polyglycerols, pentaerythritol, mannitol and other forms ofthese polyhydric alcohols when combined with polybasic carboxylic acidsof both the aromatic and aliphatic groups, with and without modificationby rosin or other natural resins or resin acids, fatty acids, vegetableoils or their equivalents. The water solutions may be diluted orconcentrated to any desired extent.

The water-soluble products described are of value for coating orimpregnating all types of non-porous or porous bodies or bodies havingporous surfaces, such as metal, glass, paper, leather, wood, concrete,gypsum tiles, wall boards, textiles, fabrics, etc. These water solutionsmay contain a single waterpoint of C.

soluble resin or mixtures of resins, either with or without additionalmaterials such as casein orother adhesives or glue-like materials suchas glues, gum arabic,'tragacanth, et}? pigments, coloring materials andthe 1i 0. 1

A coating process involving the use of a solution containing awater-soluble resin and casein is found to be particularl valuable forcertain porous bodies. A so ution was prepared by dissolving 32 parts byweight of casein in 160 parts of water and 8 parts concentrated ammonia.This solution was mixed with an equal quantity of the solution ofExample C and the mixture was applied to paper by flowing and brushing.After drying at 100 C. for five minutes it was found that the paper wascoated with a homogeneous, transparent and glossy film. To improve waterresistance, the coated paper was dipped in 40% aqueous formaldehydesolution and dried. The formaldehyde served to regenerate thewater-insoluble resin with the obvious improvement of water resistance.The proportions of resin to casein may be varied to any desired extent,although for most urposes 50 to 200% of resin based on the welght of thecasein, gives best results. The reater the resin content, the moreglossy the nished surface. I

This method of treating paper with a solution of resin and casein isparticularly valuable for the production of coated papers which are usedfor books, magazines, etc. In this connection, it is the customarpractice to admix casein with china-clay an satin-white or other mineralfillers. Such mixtures are applied in the form of sludges, the casein 1having previously been rendered soluble through use of alkalis, such assodium carbonate, borax, ammonium hydroxide, etc. However, papers coatedwith this mixture have been found to be but slightly resistant tomoisture or excessive humldity and are also quite brittle when dry. Byreplacing more 'or less of the casein with one of my watersolubleresins, I am able to prepare coated paper suitable for the purposesmentioned and having, at the same time, excellent water resistance andsuflicient flexibility. This is particularly true when the coated paperis treated to render the water-solublere5i1l insoluble as described, orin any one of a num ber of ways to be set forth.

Coatings or integral waterproofing agents for concrete and gypsumsurfaces, wall plasters, plastic paints and the like are read- 11yprepared according to the practice of my invention. Textiles or fabricsin general as well as paper may be coated and impregnated for theproduction of electrical insulation, containers, or wherever water andgrease proof surfaces are desired. Resin F and aqueous solutions thereofare specially desirable for these purposes. Cotton fabric of appropriatestructure was immersed in the solution of resin F and dried at 100 C.for a few minutes. Three coatsthusapplied resulted in a varnished fabricof value for electrical insulation and other purposes. Admixed withmineral fillers, compositions of this nature may be used for theimpregnation oz fabrics for window shades, book bindings, e c.

It is apparent that should these resins remain permanently water-solubleafter coatmg or impregnating a porous body therewith, the commercialvalue of the rocess would in some cases be questionable. owever, as hasalready been disclosed in several of the examples, the resin may berendered substantially water-insoluble after use in a number of ways.

It has been found that these resins in aqueous solution may beprecipitated and rendered substantiallywater-insolubleby the addition ofwater-soluble compounds of most polyvalent metals such as barium andcalcium hydroxides and their salts, aluminum sulfate (alum), ferrous orferric sulfates, chlorides, etc. Addition of such substances intheoretical proportions precipitate waterinsoluble resins of greathardness which have been shown to be of the nature of metallicglycerol-)hthalates and related compounds. For. instance, a process involvingthecoating of concrete or the like with the resin solutions, wouldinvolve a precipitation of the calcium salt of the resin during thecoating or impregnating operation due to the presence of lime or similarmaterials in the concrete itself. It is apparent that my rocess as wideapplicability in this connection.

Additionally, it has been observed that the ammonium ester resins may berendered water-insoluble through appropriate baking treatments attemperatures sufficiently high to cause the elimination of at least aportion of the combined ammonia.

Likewise, as described, the ammonium ester resins are found to beprecipitated and rendered water-insoluble upon the addition offormaldehyde which evidently removes the ammonia by combination to formhexamethylene tetramine. In view of this the ammonium ester resins mayhe admixed and used with the phenol-aldehyde and urea-aldehyde resins,the excess formaldehyde of these resins reacting with the combinedammonia of the ester resin to form hexamethylene tetramine which assistsin the hardening of the resulting composite, at the same time renderingthe soluble resins insoluble.

Another method for rendering the water soluble ester resins insoluble inwater comprises the addition of acids to the resin solutions or to theproducts coated or impregnated therewith. Addition of acetic,hydrochloric and other acids was observed to .a water solution 0 causethe precipitation of the insoluble .ester resins from their aqueoussolutions.

It is quite apparent from the above that the present invention issusceptible of many variations as to the details of carrying out theprocesses as well as the nature of the products treated and the resultsobtained. The bodies may be treated with the solutions in any suitablemanner, such as b brushing, spraying, flowing, dipping or ot erwiseapplying the resin solution to the body or material.

It is to be understood that the invention is not limited to the specificmatters set forth except as stated in the appended claims.

What I claim is 1. A process of treati a body which com prises applyingto a sur ace of such body, a water solution of a water-soluble salt of apolybasic acid-polyhydric alcohol resin.

2. A process of treatin a body which comprises applying to a sur ace ofsuch body, a water solution of a water-soluble salt of a polybasicacid-polyhydric alcohol resin, and rendering the resinous materialwater-insoluble.

3. A process of treating porous materials which comprises a plying tosuch materials, a water solution 0? polybasic acid-polyhydric alcoholresin.

4. A process of treating porous materials which comprises applying tosuch materials, a water solution 0 a water soluble salt of a polybasicacid-polyhydric alcohol resin, and rendering the resinous materialwater-insoluble.

5. A process of treating porous materials which comprises applying tosuch materials,

a water soluble salt of a polybasic acid-polyhydric alcohol resin, andrendering the resinous material water-insoluble by treatment with anacid material.

6. A process of treating porous materials which comprises applying tosuch materials, a water solution of a water soluble salt of a polybasicacid-polyhydric alcohol resin, and rendering the resinous materialwater-insoluble by treating with a solution of a polyvalent metal saltto precipitate a polyvalent metal salt of the resin.

7. A process of improving the water and grease resistance of paper whichcomprises coating the paper with a water solution of a water solublesalt of a resin of the polybasic acid-polyhydric alcohol type, andrendering the resin water-insoluble.

8. A process of improving the water and grease resistance of aper whichcomprises coating the paper w1th a water solution of a water-solublesalt of a resin of the polybasic acid-polyhydric alcohol type andrendering the resin water-insoluble by treatment with an acid material.

9. A rocess of preparing transparent paper w ich comprises treating thinpaper with a water solution of a water-soluble salt a water-soluble saltof a.

of a resin of the polyhydric 'alcoho'l-polybaaic acid type and renderingthe resin water-insoluble.

10. A process of preparing transparent paper which comprises treatingthin aper with a water solution of a water-solub e salt of a resin ofthe polyhydric alcohol-polybasic acid type and rendering the resinwaterinsoluble by treatment with an acid material.

11. A process of treating orous materials which comprises treating sucmaterials with a water solutioh of casein and a water-soluble salt of apolybasic acid-polyhydric alcohol resin.

12. A process of treating porous materials which comprises treating suchmaterials with a water solution of casein and a water-soluble salt of apolybasic acid-polyhydric alcohol resin, and rendering the resinousmaterial water-insoluble.

13. A process of improving the water resistance of paper which comprisescoatin the paper with a water solution of casein an a water-soluble saltof a resin of the polybasic acid-polyhydric alcohol type, and renderingthe resin water-insoluble.

14. A process of treating paper which comprises coating the paper with asludge of mineral fillers suspended in a water solution of casein and awater soluble salt of a 01ybasic acid-polyhydric alcohol resin, anrendering the resln water insoluble.

15. A process of treating porous materials which comprises applying tosuch materials, a water solution of an ammonium salt of a polybasicacid-pol hydric alcohol resin.

16. A process 0 treating textile materials which comprises applying tosuch materials a water solution 0 an ammonium salt of a polybasicacid-polyhydric alcohol-fatty acid resm.

17 A process of treating textile materials which com rises applying tosuch materials a water so ution of an ammonium salt of a linseed oilfatty acid-glycerol phthalate, and drying the coated material.

18. A composition of matter comprisin a water solution of casein and awater-solu le salt of a polybasic acid-polyhydric alcohol resin.

19. A porous article impregnated with casein and a polybasicacid-polyhydric alcohol resinous material.

In testimony whereof, I have hereunto subscribed my name this 21st dayof November,

THEODORE F. BRADLEY.

DISCLAIMER 1,780,375.The0d01'e F. Bradley, Westfield, N. J. TREATINGPOROUS AND NON- POROUS MATERIALS. Patent dated November 4, 1930.Disclaimer filed February 16, 1939, by the assignee, American Cyanam'idCompany. Hereby enters this disclaimer to claims 1, 2, 3, 4, 5, 6, 7, 8,9, 10, and 15, with the exception that your petitioner does not disclaimthe subject matter of claims 1, 2, 3, 4, 5, and 6 wherein the porousmaterials are restricted to materials other than paper.

[Ofiicial Gazette March 14, 1939.]

